Polymeric materials colored with yellow methine dyes and pigments

ABSTRACT

Polyester fabrics and rigid plastic substrates are respectively dyed and colored with a series of compounds of the formula:   WHEREIN R is hydrogen, chlorine, bromine, nitro, or acetamido; A is lower alkyl, benzyl or cyano(lower alkyl); EACH OF X and Y is independently cyano, lower carbalkoxyl   OR R1-SO2, R1 being a member selected from the group consisting of lower alkyl, chloro(lower alkyl), bromo(lower alkyl), cyano(lower alkyl), phenyl, (lower alkyl) phenyl, chlorophenyl, bromophenyl, nitrophenyl, and cyanophenyl; and X and Y taken together form a ring containing 5 or 6 ring atoms. The above compounds are useful as dyes and, according to a preferred embodiment, colorants for rigid plastic substrates.   WHEREIN W is lower alkylene or p-xylylene; EACH OF X and Y is independently cyano, lower carbalkoxyl,   OR R1-SO2, R1 being a member selected from the group consisting of lower alkyl, chloro(lower alkyl), bromo(lower alkyl), cyano(lower alkyl), phenyl, (lower alkyl) phenyl, chlorophenyl, bromophenyl, nitrophenyl, cyanophenyl; and X and Y taken together with form a ring containing 5 or 6 ring carbon atoms. In addition a further series of compounds is provided of the formula:

United States Patent [191 Renfrew [111 3,844,715 1 Oct. 29, 1974POLYMERIC MATERIALS COLORED WITH YELLOW METIIINE DYES AND PIGMENTS [75]Inventor: Edgar E. Renfrew, Lock Haven, Pa.

[73] Assignee: American Aniline Products, Inc.,

OTHER PUBLICATIONS Omelchenko et al, Chemical Abstracts vol. 56, col.6123 1962) Primary Examiner-John D. Randolph Attorney, Agent, orFirm-Armstrong, Nikaido & Wegner [57] ABSTRACT Polyester fabrics andrigid plastic substrates are respectively dyed and colored with a seriesof compounds of the formula:

wherein R is hydrogen, chlorine, bromine, nitro, or

acetamido; A is lower alkyl, benzyl or cyanol lower alkyl); each of Xand Y is independently cyano, lower carbalkoxyl ll Rr-CO or R SO R beinga member selected from the group consisting of lower alkyl, chlorotlower alkyl), bromo( lower alkyl), cyano( lower alkyl), phenyl, (loweralkyl) phenyl, chlorophenyl, bromophenyl, nitrophenyl, cyanophenyl; and

X and Y taken together with form a ring containing 5 or 6 ring carbonatoms.

In addition a further series of compounds is provided of the formula:

wherein W is lower alkylene or p-xylylene; each of X and Y isindependently cyano, lower carbalkoxyl,

or R SO R being a member selected from the group consisting of loweralkyl, chlorot lower alkyl), bromot lower alkyl), cyano( lower alkyl),phenyl, (lower alkyl) phenyl, chlorophenyl, bromophenyl, nitrophenyl,and cyanophenyl; and

X and Y taken together form a ring containing 5 or 6 ring atoms.

The above compounds are useful as dyes and, according'to a preferredembodiment, colorants for rigid plastic substrates.

4 Claims, No Drawings POLYMERIC MATERIALS COLORED WITH YELLOW METHINEDYES AND PIGMENTS BACKGROUND OF THE INVENTION The organic chemist haslong known a method for the preparation of certain methine compounds.The preparation of a specific compound [(9-ethylcarbazol- 3-yl)methylenemalononitrile], has been reported [Med. Chemie, 7 60928( 1963) 1; thiscompound has only been reported as a medicinal compound. With theincreasing requirements for better dyestuffs for polyester fabrics, aswell as the necessity of finding compounds suitable as pigments forrigid plastic substrates, the search for suitable dyestuff compounds hascontinued in recent years with great activity In accordance with theinvention, I have discovered methine compounds suitable for the dyeingof polyester fabrics, and particularly for the coloration of rigidplastic substrates.

SUMMARY OF THE INVENTION In accordance with a first aspect of theinvention, a polyester fabric material is provided. The materialcomprises a polyester fibrous material containing a methine compound ofthe formula x CH:C\ R Y wherein R is hydrogen, chlorine, bromine, nitro,or acetamido;

A is lower alkyl, benzyl or cyano(lower alkyl); each of X and Y isindependently cyano, lower carbalkoxyl,

ll E2592" W or R SO R being a member selected from the group consistingof lower alkyl, chloro(lower alkyl), bromo(lower alkyl), cyano(loweralkyl), phenyl, (lower alkyl) phenyl, chlorophenyl, bromophenyl,nitrophenyl, cyanophenyl; and X and Y taken together form a ringcontaing 5 or 6 ring atoms.

According to a preferred embodiment of the first aspect of theinvention, there are provided polyester fabric materials dyed with theabove compound wherein R is hydrogen and both X and Y are cyano.

According to a second aspect of the invention, there are provided anovel series of methines of the formula A is lower alkyl, benzyl orcyano(lower alkyl); X is cyano, lower carbalkoxy,

or R1SO2; Y is lower carbalkoxyl, i

i Il -60 X GH=C CH: X .X. .9?)

wherein W is a lower alkylene or p-xylylene; R is hydrogen, chlorine,bromine, nitro, or acetamido; each of X and Y is independently cyano,lower carbalkoxyl,

or R,SO R being a member selected from the group consisting of loweralkyl, chloro(lower alkyl), bromo(lower alkyl), cyano(lower alkyl),phenyl, (lower alkyl) phenyl, chlorophenyl, bromophenyl, nitrophenyl,cyanophenyl; and X and Y taken together form a ring containing 5 or 6ring atoms. The compounds described above as the fourth aspect of theinvention are also suitable as dyestuffs for synthetic materialsincluding polyesters.

DETAILED DESCRIPTION OF THE INVENTION The compounds of the first threeapsects of the invention may be prepared in the facile manner throughthe following synthesis. As the starting material may be used onaldehyde of the formula (III.()

(IIA) As representative aldehydes (ll) may be mentioned the followingcompounds:

9-methylcarbazolyl-3-carboxaldehyde 9-ethylcarbazolyl-3-carboxyaldehyde9-butylcarbazolyl-3-carboxaldehyde 9-benzylcarbazolyl-3-carboxaldehyde9-hexylcarbazolyl-3-carboxaldehyde9-ethyl-6-bromocarboxolyl-3-carboxaldehyde The aldehyde (II) iscondensed with a methylene of the formula:

(Ill) giro wherein W and R are as defined above.

The starting aldehyde (ll) may be produced by adding an appropriatecarbazole to dimethylformaide and phosphorus oxychloride at atemperature below about 15C. Thereafter, the mixture is heated to anelevated temperature, preferably over 90C, for a period of l-4 hours.The product is cooled and sodium hydroxy and sodium acetate addedthereto. Thereafter an aromatic solvent is added, the resultant solutionraised to the boil, and the water removed by azeotropic distillation.

The condensation reaction of the aldehyde (II) and methylene (III) isrun at a temperature of 80l44C., preferably ll25C, optionally with analcohol, such as ethanol or 2-propanol, and with a small amount ofpiperidine. After condensation is complete, which generally requiresfrom about one and one-half to four hours, the reaction mass is slowlycooled to below room temperature, preferably l0-l5C. The product dyecrystallizes slowly from the reaction mixture at these temperatures. Thedye is recovered by filtration and is subsequently washed with analcohol, such as 2- propanol, followed by cold water.

The dyestuffs made by the method of the invention are applied toaromatic polyester fibers in the form of a dispersed color powder orpaste, which is obtained by wet milling, in a conventional apparatussuch as a ball mill, the dye, a dispersant such as sodium ligninsulfonate, and a wetting agent. The dispersed cake or paste thusobtained can be dried, if desired at 7080C. and thereaftermicropulverized. Sufficient dispersant is added to give a dispersedpowder containing generally 4 between 25-40 percent by weight activedyestuff base.

The disposed powder, whenadded to water with or without auxiliaryagents, forms a near collodial aqueous dispersion from which thearomatic polyester fiber or goods is dyed in the conventional manner togive a fiber containing from 0.0l-2 percent dyestuff.

The dyes of the invention dye polyester fiber in bright shades and areapplied by carrier dyeing, pressure dyeing thermofixation methods. Thedyes also can be used for coloring nylon superpolyamide and cellulosetriacetate.

The compounds of the invention may be used for the coloration of rigidplastic substrates. The rigid plastic substrates contemplated within thescope of the invention are those plastic materials capable of beingpigmented with the compounds of the invention, and will be referred toherein as rigid plastic substrates. The rigid plastic substrates of theinvention include those materials capable of being formed into a shapedarticle, including semi-rigid materials which may be deformed byapplication of pressure.

As rigid plastic substrates of the invention may be mentionedterpolymers, including acrylonitrilestyrene-butadiene, often known asABS; acrylics, including methacrylics; polystyrene, both foamed andrubber modified; polysulfones; cellulosic derivatives, particularlyesters such as cellulose acetate, propionate and butyrate; polyamidessuch as nylon; epoxy and phenolic resins; resins; polycarbonates; andpolyesters. It is understood that the rigid plastic substrates includethose materials capable of being pigmented with the compounds of theinvention, and therefore copolymers of the above classes of compounds,such as styrenebutadiene, are also within the scope of the invention.

Specific examples of thermoplastic resins include polyvinyl chloride,polyvinyl acetate, vinyl chloride- /acetate copolymers, polyvinylalcohol, polyvinyl acetal, ethylene/vinyl acetate, ethylene/vinylpropionate, ethylene/vinyl isobutyrate, ethylene/vinyl alcohol,ethylene/methyl acrylate, ethylene/ethyl acrylate ethylene/ethylmethacrylate, ethylene/ally] alcohol, ethylene/ally] acetate,ethylene/allyl acetone, ethylene- /allyl benzene, ethylene-allyl ether,ethylene/acrole in, polyhexamethylene adipamide, polyhexamethylenesebacamide, polycaprolactam, polymethyl methacrylate, polyacrylonitrile,polymethyl acrylate. polyethyl methacrylate, and styrene/methylmethacrylate.

As preferred rigid plastic substrates of the invention may be mentionedthe polyacrylates, polystyrene and polycarbonates.

The rigid plastic substrates are colored with the compounds of theinvention through pigmentation processes. The compounds are admixed withthe plastic using sets of mixing rollers, mixing or milling apparatus.After the compounds and the plastic have been thoroughly mixed, theresultant colored mixture is shaped into the desired final form throughprocedures well known to those skilled in the art, such as pouring,calendering, extrusion, spreading, or injection molding. Where thedesired product is a semi-rigid material, plasticizers mayadvantageously be added prior to shaping into the desired final form. Asplasticizers suitable for this purpose may be mentioned esters ofphthalic acid. Although plasticizer may be incorporated after the mixingof the compound of the invention with the rigid plastic substrate, italso can be incorporated into the rigid plastic material prior to mixingthe pigment with the rigid plastic material. In order to vary thestrength of the finished product or vary the color, it is also possibleto add additional pigments or fillers in an amount sufficient to obtainthe desired effect.

The amount of the compound of the invention which is used to color therigid plastic substrate may vary widely depending upon the degree ofcolor wished to be imparted to the final product, and depending uponwhether the compound of the invention is the sole colorant or whether itis used in admixture with other plastic colorants. When the compound ofthe invention is used in admixture with other colorants, obviously avery minute quantity may be used to produce a complementary effect.Generally, the amount of colorant comprises less than l5 percent,preferably less than about 8 percent, by weight in relation to the rigidplastic substrate. An amount of colorant compound which has provedparticularly valuable is about 0.0001 percent to about 1 percent.

The following examples serve to further illustrate the invention:

EXAMPLE 1 CH=C 88.0 g dimethylformamide. To this was slowly added atl-l4C 50.6 g. phosphorus oxychloride; followed below lC 45.0 g.9-ethylcarbazole. After the addition was complete, the cooling bath wasreplaced with a water bath, and the contents of the flask were raised to9194C and held there for 3 hours. On cooling the reaction mixture formeda soft crystalline mass. To this in a suitable vessel was added 300 ml.ice and water, and slowly,

83 ml. sodiumhydroxide solution, 20 percent by weight and 265 ml sodiumacetate solution, 20 percent by weight. The pH was 6.3.

After 3 to 4 hours stirring, the supernatant fluid was drawn off and thewaxy residue was washed with three portions, each 1,500 water. Then wasadded 500 ml. toluene.

The toluene solution was transferred to a 1,000 ml.

four-neck flask equipped with a stirrer, thermometer, heater,Dean-Starke trap and condenser. The temperature was raised to the boil,and the adherent water was removed by azeotropic distillation, thetoluene being returned to the flask. After collection of water hadceased, there was added l6.2 g. malononitrile and 3.0 ml. piperidine.Heating was continued until no more water of reaction was beingcollected.

Then, l60 ml toluene was removed by distillation,

and

ml. alcohol was added to the flask. The product separated in yellowcrystals, which were collected by filtration, washed with alcohol anddried.

EXAMPLE 2 EXAMPLE 3 Methyl methacrylate resin is colored with thecompound of Example 1 as the colorant, in a ratio of 2 grams resin to 1mg colorant. The resin is prepared by placing 1 lb of methylmethacrylate into a Thropp mill (a two-roller mill), which is thenheated and run in order to melt and smash the resin to a molten mass.The compound of Example 1 is added and the entire mixture of resin andcolorant is milled until the colorant is uniformly distributed in themass as measured by eye. While still hot, 30 grams of the hot mass iscut off for use in the following procedure. The sample, containing 30grams methyl methacrylate and 15 mg. of the compound of Example 1 ascolorant, may be conveniently molded in a Laboratory 40 Single ActingWatson- Stillman Laboratory Press (Farrell-Birmingham Co. 50-ton press).30 grams of methyl methacrylate mixture containing 15 mg. of thecompound of Example 1 is placed in the cold mold, which is then closedwith the Schrader Valve. The drain is opened and steam is applied to themold. When steam comes through the drain pipe, the drain is closed. Upto 25.0 tons pressure is exerted on the chips until the mold is fullyclosed. This can conveniently be accomplished by observing the pressuregauge. When the gauge needle no longer decreases in pressure, then themold is closed.

The mold is held closed at zero pressure by releasing the hydraulicpressure and maintaining the steam for 5 minutes. The mold pressure isincreased to 10 tons and held for 10 minutes, the steam remaining on.

The mold pressure is increased to 15 tons and the steam shut off; thedrain is opened and cooling water is added for five minutes. Thereafterthe pressure is changed to zeroand the mold is opened to extract theresultant plastic chip.

EXAMPLE 4 When the 30 gram mixture of methyl methacrylate and thecompound of Example 1 are replaced by 2 pounds polystyrene, 1044 gramstitanium dioxide and 227 mg. of the compound of Example 1, following theprocedure of Example 3 a fast coloration of the polystyrene is obtained.

EXAMPLES The compound of Example I may also be used as a colorant forplastics made from polycarbonates. A pigmented plastic material ofpolycarbonates and the compound of Example 1 may be prepared accordingto the following procedure:

'7 A specimen is prepared by dry mixing pelletized or powdered resinwith finely divided colorant until uniform distribution is achieved ofthe colorant in the resin material. Plasticizer may also be added, ifdesired. The mixture is then extruded or injected molded under suitableconditions. 454 gms Lexan l2l-R (General Electric) pellets are placed inBipel one ounce reciprocating screw injection molder. The pellets aretumbled for v minutes on the barrel tumbler. The resin is heated (frontzone temperature of 550F and rear zone temperature of 500F) and chipsare produced from the virgin resin until chips of good quality areobtained. When the desired quality of chips are obtained with the clearresin, a fresh batch of Lexan l2l-R, containing the compound of Example1 in an equivalent amount corresponding to Example 2 to produce apigmented plastic material is fed into the injection molder, to produceyellow pigmented chips having excellent fastness characteristics.

A 1,000 ml. four-neck flask equipped with a stirrer,

a thermometer, a heater and a Dean-Starketrap and 3 condenser wascharged with 54.2 g. 9-benzyl-3-carbazolecarboxaldehyde, 500 ml.toluene, 14.1 g. malononitrile and 3.0 ml. piperidine. The mixture wasstirred at the boil for 5 hours; water was collected in the trap andremoved from the mixture as formed. The mixture was allowed to cool. Theyellow solid was collected on a filter, washed with first toluene, thenalcohol, and dried. M.P. 23023 1C; Analysis: N, found 13.3 percent;calc. 12.7 percent.

EXAMPLE 7 The compound of Example 6 was ball-milled with its own weightof a commerciallyavailable lignisulfonic acid dispersing agent (LignosolPTA) and enough water to make a mixture 15 percent by weight dye. Themixture was milled to a thin paste.

The paste when applied to polyester fabric by the recognized methods(carrier, pressure or thermofix) gave bright greenish-yellow dyeingswhich showed excellent sublimation and light fastness.

EXAMPLES 8-l0 By substituting an equivalent amount of the compound ofExample 6 for the compound of Example 1, otherwise following theprocedures of Examples 3-5, respectively, bright greenish yellowcolorations are obtained with methyl methacrylate, polystyrene andpolycarbonate.

EXAMPLES l 146 TABLET Example R A X Y Hue H CH CN ON Greenish yellow. 12II 11-C4H9 ON 0N D0. H n-CuHn ON ON D0.

14 H ON CN D0.

15 H --C2H CN COOC2H D0.

16 H CN COOC2H5 Do.

7 lI n-CtHn COOCzH COOC2H Do. 18 II n-CqHo CH CO COOCH DO.

10 II C:II5 CN Do.

:30 CN Same as above D0. 21 CN D0. 22 CN COOCzHs D0. 23 ON ON Do. .24 ONON D0. .25 CH3CO COOCzHs Do. 20. CN ON Do. 27 N COOC2H5 D0. 28... COOC HCO0C'JH5 D0. 20... ON ON Do. 30. CN CN D0.

Hue

Example "I ABLE lA-C0ntinued X and Y in cyclic compounds X and Yincyclic compounds w M .M v

.n 1 O C 0 0 5 0 H 3 MW R M N 3 H H 0 0 C C U h H rd 3 o a D D m Ey /m G0 0 C 0 0 0 0 0 0 C 0 c H H M 5 0 3 4 o m o D D D m N N N N m m 0 0 C o0 0 o o c 0 2 m m 5 m m m. m w c H u H m mm. B N N 0 c c 7 O H V C Wu aM n m H 4 M w N N m H V 0/ 0 k H d. C. C u w" m Io O u C N N N N 0 N N 0H 0 0 C10 OHC C||C OHC CIC C C C C U I I 1 r m w" A 1,000 ml. four-nekflask equipped with a thermometer, stirrer, and reflux condenser wascharged with OCH:

41" H CH:

13 g. malonomitrile, I g. 2-propanol and 2 ml. piperidine.

The temperature was raised to the boil and stirred at that temperaturefor 3 hours. The charge was then cooled to C. yellow crystals separatedwhich were filtered off, washed with 2-propanol, and dried. M.P.267-270C.

EXAMPLE 48-50 Thermoplastic materials such as polystyrene,polycarbonate'and methyl methacrylate, are colored in the usual way withthe material. Clear yellow hues of good light fastness are obtained onmethyl methacrylate, polystyrene and carbonate when the compound ofExample 1, otherwise following the procedures of Examples 3-5,respectively.

EXAMPLES 51-62 A is lower alkyl, benzyl or cyano(lower alkyl); each of Xand Y is independently cyano, lower carbalkoxyl.

Following the procedure of Example 47, substituting ON appropriatereactants, the following compounds are obtained. The compounds whenapplied to methyl methacrylate, polystyrene and polycarbonate by the CNmethod of Example 3-5, respectively, yield colored N plastics having thehue indicated below: (2211 A TABLE 2 R n i} Q N-w-N Y 2 X ou=o 011:0

Fx R W X Y Hue 51 II cH2 CN CN Yellow. 52 11 CH2CH2 CN CN Do. 53 HCH2(CH2)4CH2 CN CN D0. 54 H -CH2CH2CH2CH2- CN CN D0.

55 11 CN CN Do.

oH2@-om 5G 3 and 3-Cl -CH:- CN ON Do. 57 3and 3-Br CH1CH: CN 0N Do.

58 3 and 3-Cl ON ON Do.

-CH2 CH9 50 H -CH2GHgCH CN COOC2H5 Do. 60 11 OH2CH2CH2- COOCaHs ooocgmDo.

61 H CH2CH2CH3 0N D0.

62 H -CH CHzCHzcoon3 00002115 Do.

is claimed is: l. A polyester fabric material which comprises apolyester fibrous material containing a compound of t r m ls r wherein Ris hydrogen, chlorine bromine, nitro or acetamido;

1. A POLYESTER FABRIC MATERIAL WHICH COMPRISES A POLYESTER FIBROUSMATERIAL CONTAINING A COMPOUND OF THE FORMULA3-(X-C(-Y)=CH-),R,9-A-CARBAZOLE WHEREIN R IS HYDROGEN, CHLORIDE,BROMINE, NITRO OR ACETAMIDO; A IS LOWER ALKYL, BENZYL OR CYANO(LOWERALKYL); EACH OF X AND Y IS INDEPENDENTLY CYANO, LOWER CARBALKOXYL,R1-COOOR R1-SO2, R1 BEING A MEMBER SELECTED FROM THE GROUP CONSISTING OFLOWER ALKYL, CHLORO(LOWER ALKYL), BROMO(LOWER ALKYL), CYANO (LOWERALKYL), PHENYL, (LOWER ALKYL)PHENYL, CHLOROPHENYL, BROMOPHENYL,NITROPHENYL, AND CYANOPHENYL.
 2. A polyester fabric material of claim 1wherein R is hydrogen and X and Y are cyano.
 3. A polyester fabricmaterial of claim 2 wherein said compound is
 4. A polyester fabricmaterial of claim 2 wherein said compound is